JP2861389B2 - "Polyester coated fabric and manufacturing method thereof" - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyester fiber coated fabric having no disperse dye migration property and a method for producing the same.

BACKGROUND ART At present, a generally used coated fabric is a woven or knitted fabric mainly composed of nylon fibers, for example, a process of water-repellent / waterproof, moisture-permeable / water-repellent, air-permeable, flameproof / fusible coating, and the like. Various products provided with are widely used for clothing or industrial use.

However, in recent years, the price difference between nylon products and polyester products has been further increased due to soaring prices of raw materials for nylon fibers. Therefore, as an alternative to nylon fibers, the development of a coating process of polyester fibers, which is superior in features such as dimensional stability, strength, light resistance, and variety of materials, has been actively performed.

However, polyester fiber coated cloth is
There was a fatal problem that the disperse dye in the polyester fiber migrated to the coating film and was consequently contaminated.

For example, in a coated fabric of polyester fibers, when a dark color and a light or white coating surface come into contact with each other, the disperse dye on the dark color side easily migrates to the light or white coating surface, causing contamination.

The reason for this is that the fiber and the dye are not chemically bonded as in the case of acid dyeing of nylon, for example, and in the case of disperse dyeing of polyester fiber, the fiber substrate is relaxed and the dye molecules are physically The dye is completed by pushing it into the fiber substrate, and the disperse dye is soluble and has an affinity for organic solvents and synthetic resins. It is thought that it is because.

Various studies have been conducted on this problem so far. For example, in Japanese Patent Application Laid-Open No. 60-45686, aluminum, copper, fine powder of metal such as silver, potassium titanate,
There has been proposed a method of using a metal oxide such as titanium dioxide and stannic oxide and having a poor compatibility with the disperse dye to prevent the transfer of the sublimable dye. Also, Japanese Patent Application Laid-Open No. 58-4873
Patent Application Publication No. JP-B-62-53632 and JP-B-62-53632, a fiber structure obtained by forming a polyurethane resin film containing porous particles mainly composed of SiO ₂ with a water repellent having a perfluoroalkyl group. Has been proposed. Furthermore, a method of coating a resin composition containing an organometallic coordination compound has been proposed in JP-A-4-174771.

However, these conventional techniques have drawbacks such as incomplete prevention of disperse dye migration and contamination and loss of migration stain prevention performance due to washing, and have not been put to practical use at present.

Therefore, the present inventors have proposed in Japanese Patent Application Nos. 3-43789 and 4-239822 methods for making a dye colorless in a resin by utilizing the oxidizing action of a salt such as a zirconium compound. However, this method has a disadvantage that the oxidizing action of the salt is effective for the dye having a characteristic property, and the dye used for the polyester fiber structure is limited.

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned conventional drawbacks, and makes it possible to easily and stably produce a polyester fiber coated cloth having no dye transfer contamination without being limited to the type of disperse dye. It is an object of the present invention to provide a method of manufacturing by using the above method.

In order to achieve the above object, the present invention has the following configuration.

That is, it is a processed cloth obtained by coating a polyester fiber structure dyed with a disperse dye with a resin, wherein the coating resin contains an organic peroxide.

Further, a cloth obtained by coating a polyester fiber structure dyed with a disperse dye with a resin, wherein the coating resin is made of an acrylic resin or a silicone resin, and is based on the number of aliphatic protons contained in the coating resin. A polyester fiber coated fabric characterized in that the ratio of the number of protons in the aromatic ring is 1/100 or more.

Still further, the present invention provides a method for producing a polyester fiber coated fabric, comprising coating a resin solution obtained by mixing an organic peroxide onto a polyester fiber structure dyed with a disperse dye.

The polyester fiber coated fabric according to the present invention has excellent dye transfer stain fastness and excellent washing durability. On the other hand, according to the method of the present invention, very simply and without the need for special equipment,
The above-mentioned coated fabric can be stably manufactured, and the industrial effect is extremely large.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows an example of a ¹ H-NMR measurement result of an acrylic resin containing an aromatic ring which is coated on a coated cloth according to the present invention.

FIG. 2 shows an example of the ¹ H-NMR measurement result of an acrylic resin alone coated on a conventional coated cloth.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention has been completed by investigating that an organic peroxide mixed with a resin layer chemically reacts with a disperse dye and exerts a decoloring effect, It also has the durability of the performance by washing the product.

The prior art has attempted to prevent the migration of dyes such as resin coatings and fine particles having low affinity and compatibility with the disperse dye. In contrast, the present invention provides a method for chemically dispersing a disperse dye migrating from a fiber base fabric in a coating process with an organic peroxide mixed in a resin layer to make the disperse dye colorless. And has been completed by a completely new technical idea different from the conventional method. As a method for making the dye colorless, a method using hydrosulfite as reduction washing after dyeing is known. This reducing agent (hydrosulfite) is contained in a coating resin to prevent dye transfer contamination. Although a method is conceivable, the odor is strongly emitted when the product is manufactured, which is not practically preferable.

The organic peroxide used in the present invention is capable of causing a chemical reaction to colorless a disperse dye migrating from a fiber in a resin whose molecular motion is restricted. Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxyester and the like. Among them, dialsyl peroxide is preferred, and specifically, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,
Examples include 3,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and toluoyl peroxide. Particularly preferably, a diacyl peroxide having an aromatic ring such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and toluoyl peroxide is used.

In the coated fabric of the present invention, radicals are generated when the organic peroxide present in the coating resin is decomposed, and the radicals attack the disperse dye migrating from the dyed polyester fiber into the coating resin. It has the effect of decoloring.

When a diacyl peroxide having an aromatic ring or the like is used as the organic peroxide, there is an effect that an aromatic ring is present in the coating resin film, in addition to an effect of making the disperse dye to be colorless.

In the present invention, the following effects are exhibited by incorporating an aromatic ring into the coating resin.

A resin coated with an acrylic resin or a silicone resin, which is generally preferably used as a coating resin, does not originally have an aromatic ring. Therefore, these resins had poor affinity for the disperse dye. This is because many of the disperse dyes have an aromatic ring.

In the present invention, by including an aromatic ring in the coating resin, the affinity between the coating resin and the disperse dye can be increased. As a result, in the present invention, even if a dye that could not be colorless remains, an effect of suppressing the transfer of the dye in the resin by affinity is exerted.

When using a diacyl peroxide having an aromatic ring as the organic peroxide, radicals generated by the decomposition of the diacyl peroxide in the coating process attack the disperse dye that migrates from the dyed polyester fiber into the coating resin, Let it fade. In addition to the decoloring effect, the decomposed diacyl peroxide also attacks the coating resin, and the decomposed diacyl peroxide itself binds to the coating resin,
It is considered that this has the effect of adding an aromatic ring to the coating resin.

Therefore, when a diacyl peroxide having an aromatic ring is used as the organic peroxide, the aromatic ring is present in the coating resin after the coating process. This is apparent when an acrylic resin or a silicone resin, which does not originally contain an aromatic ring as a basic molecular structure, is used as the coating resin. When using a diacyl peroxide having an aromatic ring as an organic peroxide in an acrylic resin or a silicone resin, when the coating resin after the coating process is measured by ¹ H-NMR, the acrylic resin alone or the silicone resin alone appears. Absorption peaks due to no aromatic rings are observed.

The absorption peak due to the aromatic ring is observed without a significant decrease in peak intensity even when the coated cloth is dry-cleaned about 20 to 30 times.

In the present invention, the drying step of the coating process is preferably performed in a temperature range not lower than the decomposition temperature of the organic peroxide and not lower than the glass transition temperature of the coating resin.
All of the aromatic rings caused by the above-mentioned diacyl peroxide having an aromatic ring as the organic peroxide do not disappear from the coating resin due to decomposition or evaporation in such coating processing. That matter, the coating resin after coating processing ¹ H-NM
When measured by R, it becomes clear from the fact that an absorption peak due to the aromatic ring is observed.

On the other hand, when the coating resin after the coating processing of the coated cloth (conventional product) using the acrylic resin alone or the silicone resin alone was measured by ¹ H-NMR,
No absorption peak due to an aromatic ring observed in the present invention is observed. That is, this means that the organic peroxide as a polymerization initiator that may be used when producing an acrylic resin or a silicone resin does not contribute to the absorption peak due to the aromatic ring observed in the present invention. It is considered something.

Here, the “absorption peak due to the aromatic ring” is defined as ¹ H-
It is recognized by measurement by NMR. That is, the peak is measured in a CDCL ₃ (deuterium-substituted chloroform) solvent using tetramethylsilane as an internal standard, and has a chemical shift in the range of 6 ppm to less than 9 ppm.

Further, in the coated cloth of the present invention, the ratio of the number of aromatic ring protons incorporated into the coating resin to the number of aliphatic protons is 1/100 or more from the viewpoint of the affinity between the coating resin and the disperse dye as described above. It is necessary to be. Here, the `` ratio of the number of aromatic ring protons to the number of aliphatic protons '' is determined by measuring ¹ H-NMR of the resin component in the coated cloth, and tetramethylsilane is used as an internal standard, and CD
Measured in CL ₃ (deuterated chloroform) solvent,
The absorption peak observed in the chemical shift range of 6 ppm or more and less than 9 ppm is defined as an aromatic ring proton, and the integrated value is determined.
On the other hand, the absorption peak observed at 0.2 ppm or more and less than 6 ppm is defined as an aliphatic proton, the integrated value is determined, and the integrated value of the aliphatic proton is calculated with respect to the integrated value of the aromatic proton.

That is, the ratio of the number of aromatic protons to the number of aliphatic protons =
(Integral value of aromatic ring proton) / (Integral value of aliphatic proton) An example of the result of the above ¹ H-NMR measurement is shown in FIGS. 1 and 2.

Figure 1 is an acrylic resin containing an aromatic ring that is coated workpiece cloth to the coating work cloth according to the present invention ¹ H-
4 shows an example of NMR measurement results.

FIG. 2 shows an example of ¹ H-NMR measurement results of an acrylic resin alone coated on a conventional coated cloth.

Since the organic peroxide used in the present invention has a large disperse dye migration in the coating step, particularly in the drying step, the decomposition temperature by heating the organic peroxide is the same as the drying temperature in the coating step. It is preferably used. Specifically, it is preferable that at least half of the organic peroxide is decomposed during the drying time, though it depends on the selected drying temperature and drying time. More specifically, the decomposition temperature of the organic peroxide due to heating is, for example, 60 ° C.
Those having a decomposition temperature of at least 80 ° C. are more preferably used. The upper limit of the decomposition temperature is not particularly limited, but is generally about 150 ° C.

The amount of the organic peroxide to be used is preferably 0.2% by weight or more with respect to the amount of the solvent contained in the coating resin solution from the viewpoint of obtaining a sufficient effect, and 20% by weight from the viewpoint of the change of the dyed cloth and the hardening of the texture. The following ranges are preferred. More preferably, it is in the range of 0.5% by weight to 10% by weight.

The polyester fiber structure in the present invention is not limited to 100% polyester woven fabric, knitted fabric, non-woven fabric, etc., but can be any blended fabric, blended fabric, intertwisted, interwoven, interwoven and the like containing polyester fiber. However, the effect of the present invention is remarkable for a mixture of 100% polyester and a high proportion of polyester fiber.

The dyeing of the polyester woven or knitted fabric for coating used in the present invention does not require a specially limited disperse dye or special dyeing conditions, and azo dyes and dyes usually dyed with quinone dyes can be used. .

Examples of the coating resin used in the present invention include a polyurethane resin, an acrylic acid or methacrylate resin, a silicone resin, a polyvinyl alcohol resin, a vinyl chloride resin, a vinyl acetate resin or a cellulose resin, or the like. Various resin agents used for general coating processing such as a composite system can be freely selected and used. Of these, acrylic and silicone resins are preferred.

Next, a method for producing the polyester fiber coated fabric of the present invention will be described.

The polyester fiber coated fabric of the present invention is obtained by mixing and dissolving an organic peroxide in a resin solution as described above, or mixing and dissolving in a resin solution a solution previously dissolved in a solvent of the same solvent as the resin solution. The solution is obtained by coating the polyester fiber structure with the solution.

In addition, as a solvent for dissolving the coating resin, when a solvent including an aromatic ring such as toluene or xylene is used, a radical generated from an organic peroxide attacks the solvent, so that the solvent is radicalized, It is considered that the aromatic ring which is a part of the molecular structure of the solvent is bonded to the coating resin, or the solvent itself has a high molecular weight and turns into a resin. Therefore, in the present invention, the effect is increased by using diacyl peroxide or the like having an aromatic ring as the organic peroxide as described above, and further using a solvent having an aromatic ring such as toluene or xylene as the solvent. Is more preferable.

The method for coating the resin is not particularly limited, and the resin can be processed by an ordinary method.

The effect of the present invention is remarkable in a dry method in which a resin solution mixed with an appropriate amount of an organic peroxide is coated on a fiber fabric and then dried to remove the solvent. In other words, during the drying step during dry coagulation, when the disperse dye is extracted with the resin solvent from the polyester fiber dyed with the disperse dye and migrates into the resin, the disperse dye is decomposed by the organic peroxide in the resin and becomes colorless. It is done. Furthermore, the colorless dye in the present invention is colorless even if it is transferred to another resin film, and has very little contamination.

In the present invention, the reason why the above-mentioned effect is obtained is not clear, but it is presumed that the dye molecule is cleaved by an oxidation reaction or the resonance structure is changed to be colorless.

Examples Hereinafter, the present invention will be described in more detail with reference to Examples.

The evaluation of the dye transfer stain fastness in the examples was performed according to the following method.

A white cloth attached with polyester on the coated and uncoated sides of the test piece (5 cm x 5 cm) (the same fabric as the test piece coated with the same resin as the test piece, 5 cm x 5 cm)
Sandwich between the two glass plates so that the coating surfaces of the two are in contact with each other and apply a load of 4.5 kg to a thermostatic dryer (1
(20 ° C. ± 2 ° C.) for 80 minutes, and after standing to cool, the state of dye transfer from the test piece to the attached white cloth was evaluated by gray scale for contamination.

In addition, regarding the washing durability of the dye transfer stain fastness, JI
After washing according to S L1096 (method using a stirrer type washing machine), the dye transfer stain fastness was determined by the same method as described above, and the washing durability was evaluated. The results are shown in parentheses in the column of dye transfer stain fastness in Tables 1 and 2.

The ratio of the number of aliphatic and aromatic ring protons to the number of aliphatic protons in the coating resin was determined by measuring ¹ H-NMR of the resin component of the coated fabric. ¹
The H-NMR measurement conditions were determined in a CDCL ₃ (deuterium-substituted chloroform) solvent using tetramethylsilane as an internal standard, and the peak observed in a chemical shift range of 6 ppm or more and less than 9 ppm was defined as an aromatic ring proton. On the other hand, the absorption peak observed at 0.2 ppm or more and less than 6 ppm was regarded as an aliphatic proton, and the integral value was determined by the following formula. The measured values are shown in Tables 1 and 2 as “P ratio”.

Ratio of the number of aromatic ring protons to the number of aliphatic protons =
(Integrated value of aromatic proton) / (Integrated value of aliphatic proton) The following coating resins were used in Examples and Comparative Examples.

Acrylic resin (Chris Coat P-1018A: manufactured by Dai Nippon Ink Co., Ltd.) Silicone resin (Toray Silicone SD8001: manufactured by Toray Silicone Co., Ltd.) Fabrics are treated with azo-based disperse dyes (C.
1.Dispers 0-29, CIDispers R-127, CIDispers R
-167) Using 3% owf for dyeing at a temperature of 130 ° C. for 60 minutes, performing normal reduction washing, drying, and drying.
The dyed cloth for coating was obtained by performing heat set at ℃.

On the other hand, a toluene solution of an acrylic resin having a solid concentration of 15% was prepared, and benzoyl peroxide was mixed and dissolved at room temperature so as to be 5% by weight based on the solvent amount of the resin solution to prepare a coating resin solution. did.

Next, this resin solution was coated on the above-mentioned dyeing cloth for coating with a knife coater, and a film was formed by a dry method (drying at 130 ° C. × 1 minute, heat treatment at 160 ° C. × 1 minute), and a coating amount of 25 g /
An m ² coated fabric was obtained.

Table 1 shows the results of evaluating the dye transfer contamination of the coated cloth.

[Examples 2 to 4] Dry coating was performed under the same conditions as in Example 1 using the organic peroxide and the coating resin shown in Table 1.

Table 1 shows the results of evaluating the dye transfer contamination of the coated cloth.

[Comparative Examples 1 and 2] An acrylic resin (Comparative Example 1) in which benzoyl peroxide or 2,4-dichlorobenzoyl peroxide was not mixed and dissolved as an organic peroxide in the dyed cloth for coating obtained in Example 1 (Comparative Example 1), and a silicone resin Only (Comparative Example 2) was dry-coated under the same conditions as in Example 1.

Table 1 shows the results of evaluating the dye transfer contamination of the coated cloth.

As is evident from Table 1, those of Examples 1 to 4 exhibit remarkably excellent dye transfer stain prevention properties as compared with the coated fabrics containing no organic peroxide of Comparative Examples 1 and 2. I understand. Also, the washing durability was excellent.

Examples 5 to 8 and Comparative Examples 3 and 4 Examples 1 to 4 and Comparative Examples 1 and 2 except that polyester fibers dyed with a quinone-based disperse dye were used as the disperse dye.
Table 2 shows the results of the evaluation of the results obtained by preparing a coated cloth in the same manner as described above.

As is clear from Table 2, when the dyed fabric using the quinone dye was used, the dye transfer stain prevention property and the washing durability were also excellent.

Claims (5)

(57) [Claims] 1. A processed cloth obtained by coating a polyester fiber structure dyed with a disperse dye with a resin, wherein the coating resin contains an organic peroxide. 2. The polyester fiber coated fabric according to claim 1, wherein the coating resin is an acrylic resin or a silicone resin. 3. The polyester fiber coated fabric according to claim 1, wherein the organic peroxide is diacyl peroxide. 4. A fabric obtained by coating a polyester fiber structure dyed with a disperse dye with a resin, wherein the coating resin is made of an acrylic resin or a silicone resin, and an aliphatic resin contained in the coating resin. The ratio of the number of protons of the aromatic ring to the number of protons is 1/100
A polyester fiber-coated cloth characterized by the above. 5. A resin solution obtained by mixing an organic peroxide,
A method for producing a polyester fiber coated fabric, comprising coating a polyester fiber structure dyed with a disperse dye.